[0001] The present application claims the benefit and priority of U.S. Provisional Application No. 60/351,734, titled “Color Luminescence Chemical Process For Cloth Material Products”, filed on Jan. 28, 2002, the entire contents of which are incorporated herein by reference.
[0002] The present invention relates generally to luminescent products, and more specifically, to methods for manufacturing products which exhibit a daytime color and a glow in the dark color, where the glow in the dark color exhibits long term glow in the dark characteristics after absorbing energy from light sources such as sunlight, fluorescent lights and incandescent lights.
[0003] Photostorage materials such as phosphorescent materials are those that can absorb energy when excited by solar, fluorescent and other artificial lights. In particular, when these materials are excited by ultraviolet light, they deviate from their initial equilibrium states, and convert the absorbed energy to visible light after they return to the equilibrium states so as to continue to glow after the excitation has stopped. These materials are advantageous for use in a multitude of products that benefit from enhanced visibility in the dark, including household and recreational items, such as paints, clothing, material, toys, cosmetics and the like, as well as outdoor articles such as paint, road signs, decals, and safety equipment.
[0004] Luminous paints have been applied on items such as watch dials and safe marks. These paints typically exhibit a yellow-green glow and have usually been formed by admixing a photostorage or phosphorescent material, using zinc sulfide mixed with copper as an activator, into paint, ink and the like. The sulfides can absorb energy when excited by ultraviolet light with certain wavelengths and then release the energy in the form of visible light in accordance with the above light-emitting principle of the phosphorescent material. Since the sulfides, however, have a very short span of afterglow, have unstable chemical structures and are not lightproof, there exist many problems when they are used in a practical situation. For example, the visible light emitted by such materials can last only for 20-30 minutes when they are used for luminous watches. There may also be the phenomenon of light decomposition and even loss of light-emitting ability of the material when it is radiated with ultraviolet radiation. Therefore, they can not be used in outdoor environments.
[0005] To prolong the time of afterglow, radioactive materials, such as Pm, are sometimes added to give phophors light-emitting ability. However, with radioactive materials the requirement for the treatment of the materials is very strict, and high costs arise for the apparatus used and the treatment of waste materials such as waste water, so this method is not used at present. Besides sulfide phosphorescent material, it has been suggested that photostorage materials be prepared by adding the rare earth element europium to alkaline earth metal aluminates. For example, U.S. Pat. No. 3,294,699, to Lange, discloses a light-emitting material of strontium aluminate in which divalent Eu is utilized as an activator and the amount added is 2-8 mol % of strontium aluminate. This fluorescent material has a light-emitting peak of 520 nm when excited by ultraviolet light. Unfortunately, however, because this fluorescent material has little afterglow it is not suitable for use in products where a long after-glow is preferred. Additionally, this material can be problematic to use in cosmetic and other products which might come into regular and prolonged contact with skin, which could be aggravated by the phosphor composition. Furthermore, these materials are limited in their glow in the dark colors to a yellow-green glow so that they may not be suitable for a variety of applications where a specific glow in the dark color is desired.
[0006] U.S. Patent No. 5,885,483 suggests the use of a synthetic super luminescent crystal composed of aluminum oxide, strontium oxide, calcium oxide, europium oxide and boron oxide to produce luminescent products. This unique luminescent material accumulates light for high initial brightness and long afterglow duration. It absorbs light from the sun, fluorescent lights, and other light sources that excite it and glows for up to 10 hours. This product offers excellent resistance to environmental conditions, including sunlight, superior chemical resistance, and a long product life of 10 years or more. Unfortunately, this material is only available in two colors that glow in the dark—green glow and blue glow. Additionally, both are light yellow-green in day light conditions.
[0007] U.S. Pat. No. 6,177,029 discloses the use of a photostorage and emissive material having a broad range of color options. The material features high initial brightness and prolonged decay time while. The material also has daytime brightness and night time glow in the dark properties with a wide range of colors. According to the patent, one and/or two or more different fluorescent colorant and/or optical brightener materials could be combined with the luminescent material in order to create a wide range of photostorage and emissive materials of different colors. This allows the creation of custom colors for manufacturing products which provide a unique glow color appearance for improved product recognition and marketability.
[0008] Although the material described by the '029 patent provides a unique glow and color appearance, and may be used in paints, printing inks, and the like, its application to numerous commercial products can produce undesirable results in terms of texture and appearance. Additionally, the durability of commercial products, and the capacity of the products to glow in the dark for long durations, may be compromised based upon the process used to apply such a photostorage material. Therefore, what is needed are methods for manufacturing a variety of products that exhibit a daytime color and a glow in the dark color, where the glow in the dark color exhibits long term glow in the dark characteristics after absorbing energy from light sources.
[0009] The present invention overcomes the disadvantages of the prior art by providing methods for manufacturing a variety of products that exhibit a daytime color and a glow in the dark color, where the glow in the dark color exhibits long term glow in the dark characteristics after absorbing energy from light sources. Products that may be produced using the present invention include luminescent: household and recreational items, such as paints, clothing, material, toys, cosmetics (e.g., nail polish, makeup, etc.) and the like, as well as outdoor articles such as paints, road signs, decals, and safety equipment.
[0010] According to one embodiment of the present invention, there is disclosed a method of manufacturing a luminescent product that exhibits a daytime color and a glow in the dark color, where the glow in the dark color exhibits long term glow in the dark characteristics after absorbing energy from light sources. The method includes the steps of mixing at least one resin material and at least one antisettling agent to produce a resin material and antisettling agent mixture, and adding at least one luminescent crystal to the resin material and antisettling agent mixture to produce a resin and luminescent crystal mixture. The method further includes the step of mixing at least one solvent with at least one colorant to produce a solvent and colorant mixture, and combining the resin and luminescent crystal mixture with the solvent and colorant mixture, and at least one additive, to produce a luminescent material, wherein the luminescent material exhibits a daytime color and a glow-in-the-dark color.
[0011] According to one aspect of the present invention, the daytime color differs from the glow-in-the-dark color. According to another aspect of the invention, the step of combining the resin and luminescent crystal mixture with the solvent and colorant mixture and at least one additive includes the step of combining the resin and luminescent crystal mixture with the solvent and colorant mixture and at least one additive to produce a luminescent material, wherein the luminescent material includes a paint or die. Additionally, according to the invention, the at least one additive can include a plurality of glass microspheres that provide an insulting effect to the luminescent material so that the luminescent material can include an insulating paint or dye. According to yet another aspect of the invention, the step of combining the resin and luminescent crystal mixture with the solvent and colorant mixture and at least one additive includes the step of combining the resin and luminescent crystal mixture with the solvent and colorant mixture and at least one additive to produce a luminescent material, wherein the luminescent material includes luminescent tape.
[0012] Furthermore, according to the invention, the step of combining the resin and luminescent crystal mixture with the solvent and colorant mixture and at least one additive includes the step of combining the resin and luminescent crystal mixture with the solvent and colorant mixture and at least one additive to produce a luminescent material, wherein the luminescent material includes at least 50%, by volume, of the at least one resin material. The step of mixing the at least one resin material and at least one antisettling agent can also include the step of mixing the at least one resin material and at least one antisettling agent using high speed dispersion or a static mixer. Moreover, the method can further include the step of encapsulating the at least one luminescent crystal prior to the step of adding the at least one luminescent crystal to the resin material and antisettling agent mixture to produce a resin and luminescent crystal mixture.
[0013] According to yet another aspect of the present invention, the method includes the step of applying the luminescent material to an item to produce a luminescent product. According to a further aspect of the invention, the step of applying the luminescent material to the item includes using at least one applicator to apply the luminescent material, wherein the at least one applicator is selected from the group consisting of: a paint brush, a foam brush, an airless sprayer, a paint gun, a screen printer, and a dot jet printer. The luminescent material may also be heated after the luminescent material is applied to the item using the at least one applicator. Furthermore, the item may be primed with a base material, such as with a white-colored base material, prior to the application of the luminescent material.
[0014] According to another embodiment of the present invention, there is disclosed a luminescent product that exhibits a daytime color and a glow in the dark color, where the glow in the dark color exhibits long term glow in the dark characteristics after absorbing energy from light sources. The product includes a luminescent material comprising at least one resin material, at least one antisettling agent, at least one colorant, at least one additive, and at least one luminescent crystal, where the luminescent material exhibits a daytime color and a glow-in-the-dark color, and where the daytime color differs from said glow-in-the-dark color. According to one aspect of the invention, the product further includes at least one base material in contact with the luminescent material. According to another aspect of the invention, the product comprises a product selected from the list of products consisting of: nail polish, paint, fabric paint, dyes, reflective tape, road markers, road signs, outlet covers, lamp shades and apparel. According to yet another aspect of the invention, the luminescent material comprises a plurality of microspheres, wherein said plurality of microspheres provide an insulting effect to the luminescent material, where the luminescent material can comprises insulating paint.
[0015] Having thus described the invention in general terms, reference will now be made to the accompanying drawings, which are not necessarily drawn to scale, and wherein:
[0016]
[0017]
[0018]
[0019] The present inventions now will be described more fully hereinafter with reference to the accompanying drawings, in which some, but not all embodiments of the invention are shown. Indeed, these inventions may be embodied in many different forms and should not be construed as limited to the embodiments set forth herein; rather, these embodiments are provided so that this disclosure will satisfy applicable legal requirements. Like numbers refer to like elements throughout.
[0020]
[0021] Generally, the greater amount of crystals inserted into the luminescent material
[0022] According to one aspect of the invention, because the luminescent crystals
[0023] Referring again to the components of the luminescent material
[0024] The properties of the resins/substrates TABLE 1 Resins and Substrates Synthetic Resins: Natural Resins: Other Substrates Acrylic - Sandarac East India Kino - Malabar Polypropenonitrile, Guaiacum Kino, Kino Gum Polymethyl Methacrylate Storax Enamel Polyethylene Scammony Polymer - Copolymer, Allyl Resin Acaroid Resin Polyurethane, Lignin, Urea-formaldehyde Resin Animc Polyamide, Trimer Alkyd Asaftida Plastic - ABS plastic, Mylar, Phenolic Resin Camphor Thermoplastic, Bakelite, Epoxy Cannabin Teflon, Vinylite, Resinoid, Melamine Resin Amber Amino plastic, Cellulosic, Polyester Copal - Courbaril copal, Coumarone-indene resin, Vinyl Polymer - Copalite, Congo copal, Fluorocarbon plastic, Polyvinyl Acetate, Kauri, Zanzibar copal Phenolic plastic, Polyester, Polyvinyl Chloride, Dammar Polypropylene, Polyvinyl- Styrene Colophony formaldehyde, silicone Mastic resin, vinyl, Thermosetting Oleoresin - Labdanum, compositions Balsam, Canada Balsam, Turpentine, Capaiba Gum Resin - Elemi, Myrrh, Sonora Gum, Benzoin, Bdellium, Gamboge, Myrrh Wood Tar
[0025] As evidenced by the table, there are a wide variety of resins and substrates which may be used to in the luminescent material
[0026] The resins/substrates TABLE 2 Solvents Alcohols n-Amyl acetate Diisobutyl ketone Methyl alcohol Butyl lactate Cyclohexanone Ethyl alcohol Propylene glycol Isophorone n-Propyl alcohol monoethyl ether acetate Diacetone alcohol Isopropyl alcohol Methyl amyl acetate Methyl amyl ketone Isoamyl alcohol Diethyl ether Acetonitrile Cyclohexanol Diisopropyl ether Nitromethane Ethylene glycol Tetrahydrofuran Nitroethane Glycerol Cellosolve″solvent Castor oil Formamide Toluene Linseed oil Dimethyl Xylene Soya formamide Methylene chloride n-Hexane Fatty Acid Ethylene dichloride Cyclohexane Vegetable Oil Perchloroethylene VM£¦P naphtha Chlorinated Solvents 1,1,1-Tricholoro- Mineral spirits Oxygenated Solvents ethane Methyl fomate Turpentine Oxides and Glycols Ethyl acetate Acetone Water borne, e.g., H Isopropyl acetate Methyl ethyl ketone Chlorinated Solvents n-Butyl acetate Methyl isobutyl ketone Oxygenated Solvents Oxides and Glycols
[0027] The above list, though extensive, is intended to be illustrative only, and thus is not intended to limit the types of solvents, known to those of skill in the art, which are suitable for adding to the resins/substrates
[0028] Next, additives TABLE 3 Additives Additives for the crystal and pigments Wetting agent Dispersing agent Anti-floating agent Surface additives Flow agents Leveling agents Defoamers De-airaters Rheology additives Rheology modifiers Anti-setting agents Other Anti-skinning agents Preservers Driers Adhesion Promoters Catalysts Release agents
[0029] According to one aspect of the invention, glass or ceramic microspheres can constitute an additive
[0030] Finally, colorants
[0031] The selection of and methods for combining these materials
[0032] After resins and/or substrates are selected, they are mixed together using high speed dispersion or a static mixer. High speed dispersion is relatively inexpensive, but inserts air into the mixture, which is undesirable because it can affect the properties of the mixture and cause the temperature of the mixture to vary, which can impact the viscosity of the materials. On the other hand, static mixing is preferred because it introduces the least amount of air into the mixture. Additionally, when used to mix the final luminescent material
[0033] After the resins/substrates
[0034] Next, one or more solvents
[0035] After the one or more solvents
[0036] Finally, the solvent and pigment mixture is added to the mixture of the resins/substrate, antisettling agent, and luminescent crystal (block
[0037] Although the process described above is the preferred embodiment for mixing the materials that comprise the luminescent material
[0038] Luminescent Interior Wall Paint
[0039] Luminescent Crystal:
[0040] 25 grams.
[0041] Resins/Substrates:
[0042] Polyurethane, 46.4 grams; and
[0043] Acrylic, 25 grams.
[0044] Solvents:
[0045] Water, 5 grams;
[0046] Dipropylene Glycol n-Butyl Ether (DPnB), 3 grams; and
[0047] Dipropylene Glycol Methyl Ether (DPM), 1 gram.
[0048] Additives:
[0049] Leveling agent, 0.2 grams;
[0050] Antisettling agent, 5 grams;
[0051] Antifoaming agent, 1 gram; and
[0052] Glass Microsphere 6 grams.
[0053] Pigment/Colorant:
[0054] Color dependent for amount.
[0055] In this illustrative example, luminescent crystals, which provide luminous emissions in the dark, are bound in two resins/substrates. In particular, polyurethane was selected due to its flexibility, long life and resistance to chemicals and marring. This was combined with Acrylic, which accentuates the polyurethane and provide enhanced adhesion, a hard surface and relatively fast dry time, each of which are important for paint products. The resin/substrate combination is flexible, water soluble, resistant to ware, low odor, fast dry time, optical clarity, and overall appearance.
[0056] Next, water, DPnB and DPM were selected as solvents. Respectively, these materials reduce the thickness of the resins/substrates, provide a slow evaporating speed to control dry time, and prevent the coagulation of polyurethane. The additives were also selected with the end product, wall paint, in mind. The leveling agent allows for brush strokes to level out, the antisettling agent prevents caking or hard sedimentation of crystal and pigments, and the antifoaming agent takes the air out of the mixture to prevent imperfections in coatings. Additionally, glass microspheres were added to help disperse light from the luminescent crystals in an even manner. Finally, the pigment and colorant is product dependent. It provides the daytime color of the interior wall paint. Generally, any pigment or colorant that is translucent and provides color fastness is desirable.
[0057] Luminescent Nail Polish
[0058] Luminescent Crystal:
[0059] 25 grams
[0060] Resins/Substrates:
[0061] Polyurethane 75 grams.
[0062] Solvents:
[0063] Water, 10 grams;
[0064] DPnB, 4 grams.
[0065] Additives:
[0066] Leveling agent, 0.2 grams;
[0067] Antisettling agent, 3 grams;
[0068] Antifoaming agent, 1 gram;
[0069] Glass Microsphere, 10 grams, and
[0070] Thickening Agent, 0.3 grams.
[0071] Pigment/Colorant:
[0072] Color dependent for amount.
[0073] In this example the base polyurethane resin was chosen because it is extremely fast in the time it takes to set from application. It will be appreciated that this short “wet to set time” is advantageous for nail polish. Additionally, the polyurethane resin provides excellent flexibility and resistance to chemicals and marring. Therefore, the life of the nail polish is extended to 1-2 weeks, in comparison to conventional polish, which may only last 2-4 days without chipping and marring. Additionally, the resin is relatively easy to remove. The above formula allows polish to be removed without the use of a thinner, which can leave a residual staining on nails and skin. Rather, the material peals off when so desired, leaving no residue of color or material. It also has low odor.
[0074] As with the interior paint example, DPnB was selected as a solvent because it provide a slow evaporating speed to control dry time. The additives were also selected with the product, luminescent nail polish, in mind. The leveling agent allows for brush strokes to level out, the antisettling agent prevents caking or hard sedimentation of crystal and pigments, and the antifoaming agent takes the air out of the mixture to prevent imperfections in coatings. Additionally, glass microspheres were added to help disperse light from the luminescent crystals in an even manner and a thickening agent was used to increase the thickness of coating so that multiple nail polish coats are not required. Finally, the pigment and colorant is product dependent. It provides the daytime color of the interior wall paint. Generally, any pigment or colorant that is translucent and provides color fastness is desirable.
[0075] Luminescent Exterior Enamel
[0076] Luminescent Crystal:
[0077] 20 grams
[0078] Resins/Substrates:
[0079] Long oil Alkyd, 37 grams.
[0080] Solvents:
[0081] Mineral Spirits, 12.6 grams;
[0082] Additives:
[0083] Rheology modifier, 1 gram;
[0084] Antisettling agent, 5 grams;
[0085] Calcium Drier, 0.6 grams;
[0086] Zirconium Drier, 0.4 grams;
[0087] Cobalt Drier, 0.3 grams;
[0088] Anti-Skinning Agent, 0.2 grams;
[0089] Defoamer, 0.2 grams; and
[0090] Glass Microsphere, 5 grams.
[0091] Pigment/Colorant:
[0092] Color dependent for amount.
[0093] In this example the base resin, a Long oil Alkyd, was chosen for its flexibility and abundance in coatings industry. The resin is a general purpose coating that is relatively inexpensive to produce while providing good flexibility and a slow dry time. Additionally, the resin provides slow wear, which is important for exterior applications. The solvent, Mineral Spirits, is used to reduce and disperse the resin. Next, a series of additives are included to thicken the solution (rheology modifier), prevent caking (antisettling agent), to cure the Alkyd (Calcium Drier, Zirconium Drier, and Cobalt Drier), and to prevent or retard the oxidation or polymerization which results in the formation of an insoluble skin (Anti-skinning Agent). Other additives include a defoamer and glass microsphere, which perform the same functions identified in the previous examples.
[0094] Referring now to
[0095] On the other hand, according to one aspect of the invention, it is advantageous to prepare products for receiving the application of the luminescent material
[0096] After the luminescent material is applied using one of the application methods described above, the luminescent material is left to dry (block
[0097] As described above, the luminescent material
[0098] Many modifications and other embodiments of the inventions set forth herein will come to mind to one skilled in the art to which these inventions pertain having the benefit of the teachings presented in the foregoing descriptions and the associated drawings. Thus, it will be appreciated by those of ordinary skill in the art that the present invention may be embodied in many forms and should not be limited to the embodiments described above. Therefore, it is to be understood that the inventions are not to be limited to the specific embodiments disclosed and that modifications and other embodiments are intended to be included within the scope of the appended claims. Although specific terms are employed herein, they are used in a generic and descriptive sense only and not for purposes of limitation.